多孔性层状钙钛矿型镧铌酸催化剂的制备

 用正己胺预支撑层状镧铌酸,以3-丙氨基三乙氧基硅烷为硅源,将其水解后形成的硅聚合体粒子插入到镧铌酸的层间,经焙烧后制成氧化硅柱支撑的多孔性镧铌酸催化剂. 它的层间通道高度约0.52 nm,比表面积从柱撑前的5 m2/g增大到109 m2/g. 镧铌酸比表面积的显著增大,主要是由氧化硅柱撑后形成的层间狭缝状微孔孔道所提供的. 充分暴露的层间内表面使镧铌酸的酸催化性能得到大幅度改善,对异丙醇脱水的催化活性从未支撑时的32.0%提高到柱撑后的73.9%. 此催化剂的层状结构可保持到700 ℃以上,是一热稳定的多孔性层柱材料. 在催化剂制备过程中,柱化液浓度和回流反应时间对层柱材料的多孔性具有较大的影响,进而影响其酸催化活性,但这些因素不能显著改变材料的层间通道高度.     

胍盐化合物[C(NH_2)_3]_(6.3)K[Nb_(1.3)W_(10.7)O_(40)H_2]·H_2O的合成及性质

通过粉状白钨酸和可溶性铌酸钾水溶液的反应,合成了十二聚系列的钨铌杂多阴离子胍盐化合物[C(NH_2)_3]_(6.3)K[Nb_(1.3)W_(10.7)O_(40)H_2]·H_2O,研究了其水溶液的酸碱稳定性。根据红外、拉曼和紫外光谱、化学性质,认为该化合物可能具有十二聚偏钨酸根阴离子的结构骨架。     

Influence of surroundings on photorefractive effect in lithium niobate crystals

In the paper results of the investigation of the influence of electric properties of the environment surrounding LiNbO₃ crystals on photorefractive effect induced in these crystals by Gaussian Ar⁺ laser beam with various intensities are presented. We show spatial and temporal dependences of changes of the refractive index obtained experimentally in LiNbO₃: Fe and LiNbO₃: Fe:Mn samples surrounded by media with different electric conductivities and different permittivities (water, air, water solution of CaCl₂). The space and time dependences of the refractive index changes induced by the Ar⁺ laser beam are observed by means of the Mach–Zehnder interferometer using light from HeNe laser. The experimentally obtained results are in a good agreement with those following from numerical calculations using the manifold mirroring method. The agreement between calculated and experimental results indicates that the polarization charge at the photorefractive crystal/surrounding medium boundary significantly influences the photorefractive process in the crystal. The experimentally observed slow spontaneous decrease of the refractive index change in a sample placed into a slightly conducting medium (air) after switching off the beam also indicates that the polarization charge in the sample's surroundings affects the photorefraction.     

Geometric and electronic structure of positively and negatively poled LiNbO3 (0 0 0 1) surfaces

The effect of ferroelectric poling direction on the structure and electronic properties of the LiNbO₃ (0 0 0 1) surface was characterized. Low energy and reflection high energy electron diffraction indicated that both the positively and negatively poled surfaces were (1 × 1) with no evidence of longer range periodic reconstructions. Low energy ion scattering spectra from both surfaces were dominated by scattering from oxygen atoms. X-ray and ultraviolet photoelectron spectra also showed little difference between the positively and negatively poled surfaces, with the exception of a high binding energy shoulder on the O 1s core level of the negative surface. Exposure of the surfaces to atomic hydrogen caused reduction of the surface Nb rather than an increase in intensity on the high binding energy side of the O 1s peak, indicating that the shoulder on the O 1s peak on the negative surface was not due to surface hydroxyl groups. Temperature programmed desorption measurements indicated that the nearly stoichiometric LiNbO₃ samples were susceptible to loss of Li₂O starting at temperatures as low as 500 K, independent of the poling direction. An adatom/vacancy model is proposed in which oxygen ad-anions accumulate on one side of the crystal while oxygen anion vacancies are created on the opposite surface. This model can explain the apparent oxygen termination of both surfaces and the observed (1 × 1) periodicity of the surfaces, and also effectively screens the thickness dependent electric field associated with the polar orientation of the crystal.     

Efficient generation of terahertz pulses in lithium niobate crystal with integrated matching prism

We present results of experimental studies of Cherenkov-type generation of a terahertz (THz)-pulse during propagation of a femtosecond laser pulse in LiNbO₃ crystal with a Si-prism output coupler. Application of the Si-prism allows reducing essentially the damping of THz radiation because of shortening of the path of THz pulse in the nonlinear crystal. Results of experimental studies agree sufficiently well with theoretical calculations.     

Effect of the area of a lithium niobate transducer on the efficiency of ultrasonic atomization driven by resonance vibration

In recent years, individual control of one’s personal environment has been drawing increasing attention due to the growing interest in health care. Wearable devices are especially useful because of their controllability regardless of location. Humidity is one of the inevitable factors in the personal environment as a preventive against infectious diseases. Although atomization devices are commonly used as a method of humidity control, at present, there are no wearable humidity control devices. Vibration of a lithium niobate (LN) device in the thickness mode is a promising piezoelectric method for miniaturization of atomization devices for humidity control. To miniaturize the atomization device, the transducer size needs to be small not so much as to decrease the atomization efficiency. However, the effect of the device area on the atomization efficiency of LN at a size suitable for mounting in wearable devices has not been studied. Here, we conducted an atomization demonstration of LN devices with different sizes to evaluate particle size and atomization efficiency. Furthermore, to reveal the relationship between vibration behavior and atomization efficiency, resonance vibration in the MHz frequency band was evaluated by the finite element method and an impedance analyzer. The results showed that the peak size of water particles atomized by each device was in the range of 3.2 to 4.2 µm, which is smaller than particles produced by typical piezoelectric ceramics. Moreover, the best LN size for efficient atomization was found to be 8 mm × 10 mm among the five LN device sizes used in experiments. From the relationship between vibration behavior and atomization efficiency, the size of the transducer was suggested to affect the vibration mode. The obtained result suggested that the LN device is suitable for small wearable nebulizer devices.     

近化学计量比掺镁铌酸锂晶体的抗光折变性能

应用气相传输平衡技术,我们获得了3种近化学计量比掺镁铌酸锂晶体,晶体的掺镁量接近我们以前提出的第二阈值.在我们实验室所能达到的最大光强26 MW/cm2照射下,在所有近化学计量比掺镁铌酸锂晶片中没有观察到光斑畸变,该光强比同成分铌酸锂晶体所能承受的光强高6个量级,为目前已报道的铌酸锂晶体之最.应用双光束全息写入法测得掺1.0 mol; Mg近化学计量比铌酸锂晶体的光折变饱和值仅有4.6×10-7,比同成分铌酸锂晶体小两个量级,从已有实验数据推测,该晶体的抗光折变能力应当比同成分铌酸锂晶体高9个量级以上.     

新铌酸盐Ba5NdTi3Nb7O30的合成与介电性能

The New Niobate Ba₅NdTi₃Nb₇O₃₀ was synthesized by solid state reaction at 1250℃ for 48h. The crystal structure and dielectric properties of Ba₅NdTi₃Nb₇O₃₀ were determined by X-ray powder diffraction and dielectric measurements. The results show that Ba₅NdTi₃Nb₇O₃₀ belongs to ferroelectric phase of tetragonal tungsten bronze structure at room temperature with unit cell parameters: a=1.24424(4)nm, c=0.39476(2)nm, calculated density 5.719g·cm^-3. Ba₅NdTi₃Nb₇O₃₀ belongs to relaxor ferroelectrics. The phase transition temperature (T_c) of Ba₅NdTi₃Nb₇O₃₀ from ferroelectric to paraelectric is found to shift toward higher temperature side at higher fre-quency, and T_c is 90℃ at 1kHz. At room temperature, the dielectric constant (ε_r) and dielectric loss of Ba₅NdTi₃Nb₇O₃₀ decrease with the increase of frequency, and Ba₅NdTi₃Nb₇O₃₀ ceramic have high dielectric constant 489 at 1kHz.     

Structural Study of an Unusual Cubic Pyrochlore Bi1.5Zn0.92Nb1.5O6.92

Single-phase pyrochlore-type specimens of Bi_1.5Zn_0.92Nb_1.5O_6.92 were studied using combined electron, X-ray and neutron powder diffraction techniques. Rietveld refinements using neutron powder diffraction data confirmed an average pyrochlore structure A₂B₂O₆O′ (Fd&3macr;m, a=10.5616(1) Å) with both Bi and Zn mixed on the A-sites. However, refinements revealed significant local deviations from the ideal pyrochlore arrangement which were caused by apparent displacive disorder on both the A and O′ sites. The best fit was obtained with a disordered model in which the A-cations were randomly displaced by ∼0.39 Å from the ideal eight-fold coordinated positions. The displacements occur along the six 〈112〉 directions perpendicular to the O′-A-O′ links. In addition, the O′ ions were randomly displaced by ∼0.46 Å along all 12 〈110〉 directions. Crystal-chemical considerations suggest the existence of short-range correlations between the O′ displacements and both the occupancy of the A-sites (i.e., Bi or Zn) and the directions of the A-cation displacements. The combined A-cation and O′ displacements change the coordination sphere of the A-cations from 8 to (5+3); the resulting coordination environment of the A-cations bears similarities to that of the (5+1)coordinated Zn in zirconolite-like Bi₂Zn_2/3Nb_4/3O₇. The observed displacive disorder in the A₂O′ network of the Bi_1.5Zn_0.92Nb_1.5O_6.92 structure involves atoms associated with the lowest-frequency vibrational bending mode, and is likely responsible for both the high dielectric constant and the dielectric relaxation reported for this compound.